restek column

28
Inside: Introduction ..................... pg. 2 Extraction Liquid samples ................. pg. 2 Soil samples ..................... pg. 4 Cleanup ............................ pg. 5 Gel Permeation Chromatography .............. pg. 5 Analysis Calibration standards ...... pg. 6 Injection port configuration ................... pg. 6 Column selection ............. pg. 9 Reducing Discrimination ............... pg. 15 Quantitation ................... pg. 16 Summary ........................ pg. 16 Product Listing ........ pg. 17–27 Guide to Preparing and Analyzing Semivolatile Organic Compounds www.restek.com

Upload: hafisj

Post on 16-Apr-2015

56 views

Category:

Documents


0 download

DESCRIPTION

Restek Column

TRANSCRIPT

Page 1: Restek Column

Inside:

Introduction ..................... pg. 2

ExtractionLiquid samples ................. pg. 2Soil samples ..................... pg. 4

Cleanup ............................ pg. 5Gel PermeationChromatography .............. pg. 5

AnalysisCalibration standards ...... pg. 6Injection portconfiguration ................... pg. 6Column selection ............. pg. 9

ReducingDiscrimination ............... pg. 15

Quantitation ................... pg. 16

Summary ........................ pg. 16

Product Listing ........ pg. 17–27

Guide to Preparingand Analyzing

Semivolatile OrganicCompounds

www.restek.com

Page 2: Restek Column

The industry’s best technical serviceis only a phone call away! Call800-356-1688, ext. 4

(814-353-1300, ext. 4) or email us [email protected] (U.S.)

[email protected](outside the U.S.)

IntroductionThis technical guide addresses the preparation and gas chromatographic (GC) analysis ofsemivolatile organic compounds such as those listed in US Environmental Protection Agency(EPA) Methods 8270, 525, and 625; and polycyclic aromatic hydrocarbons (PAHs) such asthose listed in US EPA Methods 610 and 8100. These analyses are some of the most commontests performed by environmental laboratories, yet there are many analytical challenges ofwhich the analyst needs to be aware. For example, the samples often are highly contaminatedwith non-target compounds (e.g., hydrocarbons) and quality assurance/control (QA/QC) ofthe methods is rigorous. There are several procedures and techniques that can be employed,however, to make these analyses simpler to perform. Review this guide to learn thesetechniques and to troubleshoot analytical problems associated with the methods.

The compounds addressed in this guide are listed in Table I, but many additional compoundsare also amenable to these semivolatile methods. Table I includes the compounds cited in theUS EPA Methods, as well as some other compounds typically analyzed in environmentalsamples.

ExtractionThe compounds listed in Table I may be difficult to extract because they fall into differentchemical classes (i.e., acidic, basic, neutral, halogenated, oxygenated, polar, non-polar, low-boiling, and high-boiling compounds). Therefore, the extraction method will need to solvate awide variety of compounds. It also must recover the analytes of interest while removing theinterfering non-target contaminants. This limits the choices of cleanup options. A number ofsample extraction methods can be applied to these compounds, but only the most commonwill be addressed in this guide.

Liquid SamplesFor liquid samples, either separatory funnel extraction (US EPA Method 3510) or automatedliquid-liquid extraction (US EPA Method 3520) may be used. Separatory funnel extraction isfaster and less expensive to set up than the other methods, but it requires continuous operatorattention. Automated liquid-liquid extractors run unattended, but are more expensive and, ifanalyte recovery is lower than allowed, re-extraction by separatory funnel may be required.Alternatively, if the sample forms an emulsion to the degree that acceptable solvent recoveryis not possible using a separatory funnel, then some samples will require automated liquid-liquid extraction. Solid phase extraction (US EPA Method 3535) also is an option for aqueoussamples.

For separatory funnel extraction, measure up to 1L of water into a 2L separatory funnel andadjust the pH to >11 using 10M NaOH; be careful not to add too much base. Then extract thesample by adding 60mL of dichloromethane and shaking for two minutes. It is critical toshake all samples consistently or variations in extraction efficiency will be observed. The bestway to ensure consistency is to use a mechanical separatory funnel shaker, as there often isconsiderable variation with manual extractions. Allow the dichloromethane layer to settle tothe bottom of the funnel and then decant that layer into a collection vessel (i.e., a KurdenaDanish [KD] concentrator, or a Turbo vap or Rapid vap® container if using automatedconcentrators). This extraction step is repeated twice more to get quantitative recovery of allanalytes. Collect all three extractions into the same collection vessel and label as base/neutral.

Then adjust the water sample to a pH of slightly less than 2 using sulfuric acid (1:1, v/v).Avoid over-acidification because it can result in an acidic extract. Repeat extraction procedureon the water sample as described above, collecting extracts in a separate collection vessel andlabeling it as acid fraction.

It is critical to remove water from the dichloromethane before you concentrate the extract tofinal volume. Dichloromethane can hold approximately 11mL of water per liter ofdichloromethane. If this water remains in the extract, it will partition out when the volume isreduced. This will result in the dichloromethane boiling off first, leaving water in thecollection vessel, and the formation of a two-layer extract. The analyte recoveries will belower than desired, and the presence of water will interfere with the GC analysis.

Restek’s Customer CommitmentPlus 1™ Service means we will surpass

your expectations every time you contactus! You’ll get Plus 1™ service when youask our experienced Technical ServiceTeam to help solve a difficult analytical

problem. Our helpful, efficient CustomerService Team provides Plus 1™ service

even when you place a late-day order. Keepreaching for Restek products and service,

and we will provide you with Plus 1™

quality and attention.

Page 3: Restek Column

3

RestekTip

How to Bake Sodium Sulfate

To bake the sodium sulfate, spread itinto a glass pie plate no more than1" thick and place into a mufflefurnace at 400°C for a minimum oftwo hours. After this time, thesodium sulfate should be placed intoa glass container while still hot and

-lined cap toprevent the material fromreadsorbing contaminants from theatmosphere.

Table I. Semivolatile organic compounds listed in US EPA Methods 8270, 525, and 625.

PeakNumber Compound1 2-fluorophenol2 phenol-d63 phenol4 bis(2-chloroethyl) ether5 2-chlorophenol-d46 2-chlorophenol7 1,3-dichlorobenzene8 1,4-dichlorobenzene-d4 (ISTD)9 1,4-dichlorobenzene10 benzyl alcohol11 1,2-dichlorobenzene-d412 1,2-dichlorobenzene13 2-methylphenol (o-cresol)14 2,2'-oxybis-(1-chloropropane)15 4-methylphenol (p-cresol)16 N-nitrosodi-n-propylamine17 hexachloroethane18 nitrobenzene-d519 nitrobenzene20 isophorone21 2-nitrophenol22 2,4-dimethylphenol23 bis(2-chloroethoxy)methane24 benzoic acid25 2,4-dichlorophenol26 1,2,4-trichlorobenzene27 naphthalene-d8 (ISTD)28 naphthalene29 4-chloroaniline30 hexachlorobutadiene31 4-chloro-3-methylphenol32 2-methylnaphthalene33 hexachlorocyclopentadiene34 2,4,6-trichlorophenol35 2,4,5-trichlorophenol36 2-fluorobiphenyl37 2-chloronaphthalene38 2-nitroaniline39 dimethyl phthalate40 2,6-dinitrotoluene41 acenaphthylene42 3-nitroaniline43 acenaphthene-d10 (ISTD)44 acenaphthene45 2,4-dinitrophenol46 4-nitrophenol47 dibenzofuran48 2,4-dinitrotoluene49 diethyl phthalate

PeakNumber Compound50 fluorene51 4-chlorophenyl phenyl ether52 4-nitroaniline53 4,6-dinitro-2-methylphenol54 N-nitrosodiphenylamine55 2,4,6-tribromophenol56 4-bromophenyl phenyl ether57 α-HCH58 hexachlorobenzene59 β-HCH60 pentachlorophenol61 γ-HCH (Lindane)62 phenanthrene-d10 (ISTD)63 phenanthrene64 anthracene65 δ-HCH66 carbazole67 heptachlor68 di-n-butyl phthalate69 aldrin70 heptachlor epoxide71 fluoranthene72 endosulfan I73 pyrene74 4,4'-DDE75 p-terphenyl-d1476 dieldrin77 endrin78 endosulfan II79 4,4'-DDD80 endrin aldehyde81 butyl benzyl phthalate82 4,4'-DDT83 endosulfan sulfate84 endrin ketone85 methoxychlor86 3,3'-dichlorobenzidine87 benzo(a)anthracene88 chrysene-d12 (ISTD)89 chrysene90 bis(2-ethylhexyl)phthalate91 di-n-octyl phthalate92 benzo(b)fluoranthene93 benzo(k)fluoranthene94 benzo(a)pyrene95 perylene-d12 (ISTD)96 ideno(1,2,3-cd)pyrene97 dibenz(a,h)anthracene98 benzo(g,h,i)perylene

The optimum way to remove the water is to decant the dichloromethane through granularsodium sulfate, which is held in a funnel with a high-quality grade filter paper (e.g.,Whatman® 541). Approximately 30g of sodium sulfate are sufficient for most samples. Thisstep must not be skipped. Methods may call for powdered sodium sulfate, but some analytescan be adsorbed onto the smaller particles so it is recommended that only 10-60 mesh orsimilar granular sodium sulfate be used. Also, it is important that this material be contami-nant-free, so it should be purchased as American Chemical Society (ACS) pesticide residue-grade in glass containers or baked in a muffle furnace if purchased in bulk packages whereexposure to plastic is an issue (see Restek Tip). If a muffle furnace is not available, thesodium sulfate can be washed or extracted with dichloromethane prior to use; however thistechnique uses large amounts of solvent.

sealed with a PTFE

Page 4: Restek Column

4

Automated liquid-liquid extraction can run unattended once the samples are ready and thesolvent is added. This extraction is performed at a single pH. Generally, you will need toadjust the sample pH to 2, but some methods call for adjusting the pH to 4. In any event, it iscritical to not let the pH go below 2 when using a liquid-liquid extractor. If this happens, anacidic extract will form and may cause damage to the GC column. Acidic extracts also willcause low recoveries for the late-eluting internal standards, possibly due to isotope exchange(e.g., perylene-d12).

Automated liquid-liquid extractors are available in two versions—conventional and acceler-ated. The conventional types use 1L of sample and extract using 100 to 500mL ofdichloromethane. These extraction vessels typically are operated for 16 to 24 hours in order toachieve complete extraction. The accelerated extractor uses a hydrophobic membrane toseparate the aqueous from the organic phases, and the extraction time can be reduced by 25 to30% compared to the conventional extractor. However, the membranes are expensive, so it isimportant to analyze the cost versus the number of samples extracted to determine if there is acost benefit to using this accelerated technique.

Finally, solid phase extraction (SPE) also may be used to extract semivolatile organiccompounds from aqueous samples. When using SPE, it is extremely important to follow themanufacturer’s recommendations for product use. There are several manufacturers of C18cartridges and disks, which are the typical media for these compounds. The specific steps toextract these compounds will vary somewhat depending on the manufacturer. One of thebiggest problems with SPE is plugging of the disk or tube with suspended solids, so thismethod only works reliably for drinking water samples. If contamination levels are low andthe samples are free of solids, SPE provides very fast extraction times and low solvent usage.It is used easily for field extractions. And, generally, the disks are preferred for the extractionof 1L sample volumes, but recoveries are not uniform for all of the compounds in Table I. Thecompounds listed in US EPA Method 525.2 exhibit good extraction recoveries using thistechnique. For detailed information on this extraction, request the Applications Note “SPEExtraction for US EPA Method 525.1” (lit. cat.# 59557).

Soil SamplesSoxhlet and ultrasonic extraction are the most common extraction techniques for solid samples;although pressurized fluid, microwave, and supercritical fluid extraction (SFE) also can be used.

Because the soil and biota samples essentially are wet particles, acetone and dichloromethane(1:1) usually are used as the extraction solvents. Acetone is needed to adequately penetrate thesoil particle so that compounds in the particle can be extracted. Several other solvent systems areused for more specialized extractions, but for most applications this combination works well.

All solvents used for extractions must be ACS pesticide-residue grade, and a solvent assayshould be performed to verify purity prior to use. To perform a solvent assay, evaporate 300 to400mL of solvent to a final volume of 1mL and analyze by GC/mass spectrometry (MS). Theresulting chromatogram should have no compounds quantitated above 1/2 the detection limitfor any target compound.

Soxhlet and ultrasonic extraction work well for the semivolatile compounds listed in Table I.Sonication is a faster technique but requires constant operator attention. In both techniques,problems usually are caused by contaminated reagents (especially sodium sulfate) or byinconsistent handling from sample to sample. Sodium sulfate must be treated to remove wateras described in the Restek Tip on page 3, and the sample must be mixed with the sodiumsulfate to achieve a sandy consistency.

Pressurized fluid extraction (US EPA Method 3545A) can be run in an unattended fashionwith multiple samples across a wide sample size range. Extraction vessels with volumes of 1to 100 mL are available. Instruments like the Dionex ASE 200 accommodate wet samplesfrom 1 to 15 grams, and the Dionex ASE 300 will accommodate wet samples from 15 to 50grams. The volume of the cell needed for wet samples is generally twice the gram weight ofthe sample being used. For example, if 30-g wet samples are needed, the 66-mL and 100-mLvessels will be adequate for these extractions. This is necessary because a drying agent such

RestekTip

Clean Glassware

It is important to properly cleanglassware used during sampleextraction. Contaminated glasssurfaces can react with samples andcause breakdown or adsorption ofactive compounds. Verify cleanlinessby running blanks through allglassware.

Page 5: Restek Column

5

RestekTip

Stabilizing Dichloromethane

Dichloromethane requires a stabilizer toprevent the formation of hydrochloricacid (HCl). Without a stabilizer, HClwill form and injection of acidicdichloromethane will cause inlet linersand columns to become reactive. Thereare two types of stabilizers: stabilizersthat keep HCl from forming, andstabilizers that eliminate HCl uponformation. Methanol is a stabilizer thatprevents HCl from forming; whereascyclohehane, cyclohexene, 2-methylbutene, and amylene scavengethe HCl after its formation.

Dichloromethane used in liquidextractors should contain both types ofstabilizers. Methanol is a betterstabilizer, acting as a free radicalinhibitor, but methanol partitions intothe the water phase. This could leave anunstabilized extract unless a scavengerstabilizer also is used.

as diatomaceous earth is added to the sample prior to being loaded into the extraction vessels.The type of samples being extracted as well as the required method detection limits should beconsidered as part of the evaluation of pressurized fluid extraction.

Microwave extraction (US EPA Method 3546) can be useful for automated extraction as well.This method typically performs the extraction of 12 samples simultaneously, but requires slightlymore operator handling than the pressurized fluid extraction instruments. Microwave extractioninstrumentation is less expensive, but can suffer from the same sample size limitations.

Supercritical fluid extraction (SFE) has been promoted for a number of years as a means of“solventless” extraction for environmental samples. SFE has been added to SW-846 asMethods 3560, 3561, and 3562 but its application is limited. SFE suffers from severe matrix-related variation, requiring modification of its conditions depending on soil type, watercontent, sample size, and type of analytes. Doing so ultimately requires additional samplepreparation prior to the actual extraction. These requirements, added to the high cost of theinstrument, have virtually precluded the use of SFE for environmental sample preparation.

CleanupSample extract cleanup may be the most important step in maintaining long-term instrumentperformance. Many times, when instrument problems arise, they are caused by exposure ofthe injection port and the column to material in the sample extracts other than the targetcompounds. While all contaminants cannot be eliminated, reducing them will minimizeinjection port and column maintenance. Most semivolatile extracts, especially those extractsfrom soil and biota samples, contain high-boiling hydrocarbons and lipids. The difficulty inattempting to remove these compounds using one of the common solid-liquid cleanuptechniques (e.g., Florisil® and silica gel) is that the cleanup technique also removes some ofthe target compounds. In addition, because the analytical method usually calls for thereporting of several tentatively identified compounds (TICs), it is not desirable to clean theextracts of compounds that would normally elute in the range of the target compounds. Forthese reasons, gel permeation chromatography (GPC) is the only universal cleanup techniquefor semivolatile extracts.

Gel Permeation ChromatographyGel permeation chromatography (GPC) is a preparative scale chromatographic method ofseparation based on molecular size. Because the target compounds are similar in molecularsize, they elute as a band of material and are easily separated from lighter and heaviercontaminants. However, GPC systems are expensive and the processing time per sample isbetween 30 to 70 minutes. For these reasons many laboratories choose not to use GPC.However, it is very efficient for removing sulfur, high molecular weight hydrocarbons, andlipids from semivolatile extracts; and may be prudent for soil and biota samples.

Although sulfur can be removed using other techniques such as mercury or activated copperpowder, these procedures, especially copper powder, may degrade some of the target compoundsand will not remove the high-boiling hydrocarbons or lipids. The lipid content of biota extractscan be significant and may overload most SPE clean-up techniques. If a sample extract with ahigh lipid content is injected into the GC, the injection port and front of the column will becomecontaminated quickly. This will result in failure of check standards and the loss of activecompounds such as nitroanilines, nitrophenols, carbazole, and pentachlorophenol (PCP). In spiteof the added expense and time required for GPC, it is the best alternative for extract cleanup.

US EPA Method 3640 details the requirements for GPC cleanup of extracts for semivolatileanalysis. One of the important steps of GPC cleanup is to ensure each day that the instrumentis within its retention time calibration. Although not required by the method, it is goodpractice to run a daily calibration check standard before processing the next batch of samples.If a number of samples have been processed that contain large amounts of contamination, thefront of the GPC column can become reactive. This typically is observed in the loss of 2,4,6-tribromophenol for semivolatile extracts. If the column becomes reactive, injecting blanksmay return the system to control and save the time required to change the column.

Page 6: Restek Column

6

Obtaining consistent GPC results begins with the extraction and concentration proceduresbecause slight changes in mobile phase and sample solvent composition can result in sometarget compounds being uncollected. Because the typical sample solvent for GPC is puredichloromethane, it is critical that all extracts be reduced to as small a volume as possiblebefore reconstitution in dichloromethane to avoid large amounts of acetone being applied tothe column. Soil and biota samples typically are extracted with a solvent mixture of acetoneand dichloromethane. It is critical that all extracts be reduced to as small a volume as possiblebefore reconstitution in dichloromethane to avoid large amounts of acetone being applied tothe column. Dichloromethane has a lower boiling point than acetone, so it will evaporate firstduring sample concentration, which will leave nearly 100% acetone in the concentrationvessel. If dichloromethane is then added to adjust the extract to volume, there will besignificant amounts of acetone introduced to the GPC column. This will lead to “solventshock” and the formation of a void will be observed at the front of the column. This, in turn,will affect the retention times of the compounds eluting from the GPC column and ultimatelywill result in some target compounds being uncollected. Table II lists the commonsemivolatile compound elution volumes using GPC.

Analysis

Calibration StandardsCalibration standards are purchased as mixtures and usually are divided among three to sevenseparate ampuls due to the cross-reactivity of several compounds. It is important whenmaking the actual working standard that the solution be stored under refrigerated conditions ina Mininert™ vial (Restek cat.# 21050 and 21051) due to the volatility of some of the com-pounds. Failure to properly store the calibration standards will result in evaporative loss of theearly-eluting compounds and the solvent. This will, in effect, concentrate the late-elutingcompounds and cause continuing calibration failure and quantitation errors. Even when storedunder the correct conditions, there still will be degradation of some compounds due to cross-reactivity. This is observed as a loss of the target compound and commonly occurs withbenzidine, 3,3'-dichlorobenzidine, 4-chloroanaline, N-nitrosodiphenylamine, and to a lesserextent with the phenols and other anilines. These standards are stable in the separate ampulssupplied from the manufacturer, but problems arise when all of the compounds are mixedtogether to make the working calibration standard. Therefore, it is important to monitor theresponse of the more active compounds and make fresh mixtures when the calibrationstandards degrade.

Injection Port ConfigurationSeveral of the compounds listed in Table I are prone to breakdown or adsorption on activesurfaces. Typically this will occur in the injection port; therefore, careful attention must begiven to the configuration and maintenance of the injection system.

On-column injection techniques can eliminate breakdown or adsorption in the injectionsystem and improve chromatographic analysis for drinking water extracts or extracts withlittle or no non-volatile residues. However, we do not recommend on-column injections forsoil and biota extracts or extracts that contain large amounts of non-volatile residue, becausethe analytical column can be contaminated quickly.

The preferred injection technique for analyzing highly contaminated extracts is direct injection,but direct injection can cause solvent peak tailing and result in some of the target compoundseluting close to the solvent peak.

To reduce solvent peak tailing, splitless injection is most commonly used for GC/MS analysis ofsemivolatile compounds. There are some drawbacks to splitless injection including molecularweight discrimination, incomplete sample transfer, and reactivity. These problems can beminimized if the technique is properly optimized. Splitless injection requires an injection systemthat is equipped with a solenoid valve controlling the flow to a split vent. The solenoid valve isclosed during the injection process, so the majority of the vaporized sample moves to the front of

RestekTip

Mixing Calibration Standards

When blending several ampuls toproduce a calibration standard, it isimportant that all the compounds arecompletely dissolved in the solvent.This is particularly important withsome of the high molecular weightpolycyclic aromatic hydrocarbons(PAHs) and pesticides that canseparate from solution duringrefrigerated storage. Before openingampuls containing semivolatilecompounds, allow them to warm toroom temperature. Some mixturesmay require sonication to ensurecomplete solubility. Follow themanufacturer’s recommendations forproper handling of the standardmixture. Because some semivolatilecompounds are light sensitive, it isrecommended that calibrationstandards be stored in amber vials.

Page 7: Restek Column

7

Table II. Mobile phase volumes for elution of semivolatile compounds by GPC.

Compound Elution Volumes (mL)Start End

2-fluorophenol 201 241

phenol-d5 201 249

phenol 209 225

bis(2-chloroethyl)ether 201 225

2-chlorophenol-d4 209 249

2-chlorophenol 209 241

1,3-dichlorobenzene 225 257

1,4-dichlorobenzene-d4 225 257

1,4-dichlorobenzene 225 257

1,2,-dichlorobenzene-d4 225 257

1,2-dichlorobenzene 225 257

2-methylphenol 201 241

2,2'-oxybis(1-chloropropane) 201 225

4-methylphenol 201 241

N-nitroso-di-n-propylamine 186 217

hexachloroethane 233 257

nitrobenzene-d5 209 233

nitrobenzene 209 233

isophorone 193 217

2-nitrophenol 217 233

2,4-dimethylphenol 201 225

bis(2-chloroethoxy)methane 193 225

2,4-dichlorophenol 201 241

1,2,4-trichlorobenzene 225 257

naphthalene-d8 225 249

naphthalene 225 249

4-chloroaniline 217 241

hexachlorobutadiene 225 249

4-chloro-3-methylphenol 201 225

2-methylnaphthalene 225 249

hexachlorocyclopentadiene 225 241

2,4,6-trichlorophenol 201 249

2,4,5-trichlorophenol 201 249

2-flurorbiphenyl 217 241

2-chloronaphthalene 233 249

2-nitroaniline 209 233

dimethylphthalate 193 217

acenaphthylene 225 257

2,6-dinitrotoluene 193 225

Compound Elution Volumes (mL)Start End

acenaphthene-d10 225 249

3-nitroaniline 209 225

acenaphthene 225 249

2,4-dinitrophenol 201 225

dibenzofuran 225 249

4-nitrophenol 201 217

2,4-dinitrotoluene 201 225

diethylphthalate 186 209

fluorene 225 241

4-chlorophenyl-phenylether 217 241

4-nitroaniline 201 225

4,6-dinitro-2-methylphenol 201 225

N-nitrosodiphenylamine 201 233

2,4,6-tribromophenol 217 249

4-bromophenyl-phenylether 217 241

hexachlorobenzene 233 257

pentachlorophenol 209 249

phenanthrene-d10 225 257

phenanthrene 225 257

anthracene 225 257

carbazole 225 257

di-n-butylphthalate 178 201

fluoranthene 225 257

pyrene 225 257

terphenyl-d14 217 233

butylbenzylphthalate 178 201

benzo(a)anthracene 225 257

3,3'-dichlorobenzidine 209 241

chrysene-d12 225 257

chrysene 225 257

bis(2-ethylhexyl)phthalate 162 186

di-n-octylphthalate 162 186

benzo(b)fluoranthene 225 265

benzo(k)fluoranthene 225 265

benzo(a)pyrene 225 265

perylene-d12 249 273

indeno(1,2,3-cd)pyrene 241 273

dibenz(a,h)anthracene 225 257

benzo(g,h,i)perylene 233 273

Standard prepared and loaded as 1/4 acetone, dichloromethane; 5mL sample loop;Column: 70g SX-3 silica size exclusion packing; Guard column: 5g same packing;Flow rate: dichloromethane at 5.3mL/min. at 13 psi; Samples analyzed by GC/MS.

(US EPA 8270 )

the column. After a short time the solenoid valve is opened to allow excess solvent vapor to exitthe split vent. The process of transferring the sample onto the column is relatively slow duringsplitless injection, so the sample must recondense at the front of the column through solvent oranalyte focusing. This is accomplished by having the starting oven temperature 20°C lower thanthe boiling point of the solvent or the first eluting compound.

Page 8: Restek Column

8

Figure 1. Optimizing splitless hold time.

0 15 30 45 12075 90 10560

late-eluting compounds

hold time (sec.)

20

16

12

8

4

0

com

pone

nt a

rea

(tho

usan

ds)

The time period that the solenoid valve is closed is referred to as the splitless hold-time.The hold-time must be optimized to obtain the best performance from the analytical system.If the solenoid valve is opened too quickly, some of the sample will be lost causing reducedresponse. If the solenoid valve is open too long, the solvent peak will tail. The splitless hold-time will vary depending on column flow rate, injection port geometry, injection porttemperature, and volatility of the analytes. It is impossible to predict the optimum splitlesshold-time without performing some experimentation under the exact conditions of youranalysis.

To optimize the splitless hold time for a particular instrument, prepare a standard that containsboth an early- and a late-eluting compound (e.g., fluorophenol and benzo(g,h,i)perylene).Inject this standard over a range of splitless hold times from 0.1 to 2.0 minutes and plot thedata. An example of this optimization is shown in Figure 1.

In this example the optimum splitless hold time is 60 seconds. This is the point on the graphwhere the response of the late-eluting compound levels off. Holding the solenoid valve closedlonger will not appreciably increase the response of this compound, but will greatly increasethe size of the solvent peak. Because the lower boiling compound will transfer onto thecolumn faster, its response will level off sooner (in this example ~45 seconds). Once this datahas been plotted, it is possible to observe the correct splitless hold-time (once again, the pointat which the response of the late-eluting compounds levels off). The net effect of thisoptimization is to maximize response of late-eluting compounds while minimizing solventtailing.

In addition to optimizing the splitless hold-time, fused-silica wool should be used in theinjection port liner to improve vaporization of higher molecular weight compounds. Whilethere are different theories regarding the placement of fused-silica wool, consistency in theamount of packing and location of the packing is most important. Restek recommends placingthe plug of wool below the point that the syringe needle reaches, but above the inlet of thecolumn. We also recommend using a gooseneck liner to minimize contact between theinjected sample and the bottom of the injection port. This will help improve the response ofthe more reactive compounds such as 2,4-dinitrophenol, PCP, and the nitroanalines. Thegooseneck liner also makes the greatest improvement in response and minimization of endrinbreakdown for US EPA Method 525.

Another technique to minimize molecular weight discrimination is to perform the splitlessinjection under a higher column head pressure. A high inlet pressure is advantageous duringinjection to control the rapidly expanding vapor cloud in the inlet. By using a momentarypressure pulse for the time that the split vent line is closed, the sample vapor cloud iscontrolled and sample backflash into the gas lines entering and exiting the injection port isminimized. The effect of the pressure pulse is to increase the amount of analyte transferred tothe column, especially the late-eluting components. This can lead to stationary phaseoverload, however, so it may be necessary to increase the capacity of the column when usingthis technique (see the Column Selection section for more information).

early-eluting compounds

Page 9: Restek Column

9

Table III. Recommended installation distances.

Figure 2. The Rtx®-5Sil MS column structure.

Agilent (HP): 5-7mm from tip of ferruleVarian 1075/1077: 5.7cm from back of nutPerkinElmer Autosystem: 4.5 - 5.0cm from back of nutShimadzu 14A: 4.0cm from back of nutShimadzu 17A: 35mm from tip of ferrule

split: 40mm from back of nutsplitless: 64mm from back of nut

Any injection technique can suffer from reactivity (i.e., breakdown) and splitless injection isno exception. The splitless technique has two primary mechanisms for compound reactivity:sample backflash into the gas lines that enter and exit from the injector; and exposure of thesample extract to active sites on the wool, liner, and tip of the column. In general, the same setof compounds break down regardless of which mechanism is occurring: 2,4-dinitrophenol,PCP, 4-nitrophenol, carbazole, and 3-nitroaniline.

Daily maintenance of the injection port will help decrease this problem. Replace the inlet linerand fused silica wool plug, and the septum every day. Weekly, or more often depending on theextract contamination level, replace the inlet seal and remove a short section from the front ofthe column. The length of column removed will vary depending on the level of contaminationin the extracts, generally 6 to 12 inches is adequate. When cutting the column and re-installingit into the injection port, be sure to make a square cut and be consistent with the installationdistance. The installation distance varies by manufacturer. Refer to Table III for a list ofrecommended insertion distances.

Column SelectionDue to the wide variation in functionality, volatility, and polarity of semivolatile compounds,it is not possible to select a column that is highly selective for all of them. As a result, thisanalysis is performed on a general-purpose stationary phase. The Rtx®-5Sil MS column hasthe best combination of low bleed, high inertness, and efficiency for semivolatile applications.(The Rtx®-5MS column also has been successfully used for analysis of semivolatile com-pounds.) The Rtx®-5Sil MS column features a silarylene phenyl/methyl phase that wasdeveloped to provide lower bleed and greater efficiency than other “5-type” phases forimproved separation of the PAHs (Figure 2).

Low-bleed columns are necessary for the more sensitive instruments. For laboratories usingthe Agilent 5973 GC/MS or ion trap MS, column bleed can be a very important issue. Asthese instruments have become more sensitive, the higher-bleed columns produce a larger

signal on the detector and cancause electron multiplier satura-tion. If this occurs, calibrationcurves may show non-linearity athigher concentrations. This issometimes referred to as high-endroll-off, when the signal for agiven concentration is lower thanexpected due to detector satura-tion. (See Quantitation section formore information on high-endroll-off.)

To diagnose column bleed problems, make an injection that allows the bleed to be measuredrelative to the concentration of the analyte in the method. Many data systems will normalizethe display to the largest peak in the analysis. If no compounds are injected, the display willfalsely indicate a high background. The Rtx®-5Sil MS column shows a minimal bleed levelfor a 20ng per component standard (Figure 3).

Page 10: Restek Column

10

Figure 3. The Rtx®-5Sil MS column exhibits low bleed at 20ng concentration level.

Detector saturation also can be caused by the concentration of the analytes. It was commonpractice on older, less sensitive GC/MS systems to increase the multiplier voltage above the tunevalue to improve sensitivity of low-concentration standards. This technique can lead to problemswith the newer, more sensitive instruments. It is much more likely the higher concentrationcalibration standards will saturate the new GC/MS systems. It may be necessary to reduce themultiplier voltage below the tune value if high-end roll-off is observed. High-end roll-off alsomay be observed when using pressure-pulsing injection techniques to minimize high molecularweight discrimination. If this is observed, you may either increase the stationary phase filmthickness, or increase the column diameter. Alternatively, you may modify the injectionconditions to eliminate the source of the overload.

Column capacity also must be addressed when optimizing the analysis. The typical calibrationrange for many of these methods is 20 to 160ng per compound. This requires a column stationaryphase and diameter that will not overload with a 160ng or larger injection. Because there is a lossof analyte in any splitless injection, calculation of the necessary column capacity is not simple. Ifthe injection has been optimized for splitless hold-time and fused silica wool is being used in theliner to minimize high molecular weight discrimination, then it is easier to overload the analyticalcolumn. Possibly the biggest cause of overload is from pressure-pulsing the injection port, as thisimproves the transfer of all compounds to the column. The required capacity for your system willbe a function of the specific calibration standards and, more importantly, the injection port.

From a capacity consideration, a 0.25mm ID column with 0.25µm film thickness does nothave sufficient capacity for a 160ng per component standard. Figure 4a shows the poor peakshape observed when a column is overloaded. Increased capacity can be achieved byincreasing column diameter or film thickness.

When increasing column diameter, the flow rate of the column can be a concern with bench-topGC/MS systems. Many bench-top GC/MS systems do not have the pumping capacity for thecarrier gas flow that is needed with a 0.32mm ID column. A 0.28mm ID column can increasesample capacity without exceeding the pumping capacity of most bench-top GC/MS systems,making it ideal for calibrating semivolatile compounds from 20 to 160ng without overload.Alternatively, a 0.25mm ID column with a 0.5µm film thickness also has sufficient capacity tohandle a calibration from 20 to 160ng without exhibiting overload. Figure 4b shows excellentpeak shape for a 160ng-per-component standard on a 30m, 0.25mm ID, 0.5µm Rtx®-5Sil MScolumn.

The total analysis time should be as short as possible without sacrificing separation orresolution between compounds with similar mass spectra. Pay particular attention to theseparation between benzo-b- and benzo-k-fluoranthrene—they tend to be the most difficult-

1 2

3

4

56 7

19 20 21 22 23 24 25 26 27 28 29 min.

1. benzo(b)fluoranthene2. benzo(k)fluoranthene3. benzo(a)pyrene4. perylene-d125. indeno(1,2,3-cd)pyrene6. dibenz(a,h)anthracene7. benzo(g,h,i)perylene

30m, 0.25mm ID, 0.5µm Rtx®-5Sil MS (cat# 12738)20ng splitless injection of CLP standard; GC: HP/Agilent 6890 w/ 5973 mass selective detector, scan range 35-550

AMU; Oven program: 40°C (hold 2 min.) to 290°C @ 20°C/min. (hold 0 min.) to 303°C @ 2°C/min. (hold 0 min.) to330°C @ 6°C/min. (hold 1 min.); Carrier gas: He @ 1.0mL/min. constant flow; Inj. temp.: 300°C; Det. temp.: 280°C

Page 11: Restek Column

11

Figure 4a & 4b. Avoid overload by selecting a column with the proper capacity.

1

2

3

4

5

6,7

8

1

2

3

4

5

6,7

8

Peak List for Fig. 4a & 4b1. di-n-octyl phthalate2. benzo(b)fluoranthene3. benzo(k)fluoranthene4. benzo(a)pyrene5. perylene-d126. indeno(1,2,3-cd)pyrene7. dibenz(a,h)anthracene8. benzo(ghi)perylene

4aPoor peak shape for a0.25mm ID, 0.25µm

Rtx®-5Sil MS column

4bExcellent peak shape for a

0.25mm ID, 0.5µmRtx®-5Sil MS column

to-separate analytes, sharing common mass spectra and quantitation ions. Figure 5 shows a80ng per component injection of the compounds listed in Table I with an analysis time under30 minutes. The expanded sections of the chromatogram show the excellent resolution thatcan be achieved with the Rtx®-5Sil MS column.

In the past, the GC/MS systems used for semivolatile analysis did not have the sensitivity forsplit injections, so laboratories were limited to splitless injection. Newer systems such as theAgilent 5973 and ion trap GC/MS have greatly improved sensitivity, which allow the use ofsplit injection and still meet the detection limits required by most semivolatile methods.Figure 6 shows the 20ng per component standard injected in split mode using a 20:1 split ratioon a 30m, 0.25mm ID, 0.25µm Rtx®-5Sil MS column. The low bleed exhibited by thiscolumn is critical when working with these more sensitive GC/MS systems. A benefit of splitinjection is narrower peak widths for improved separations between closely eluting com-pounds. Also, split injections usually result in less reactive compound breakdown because theresidence time in the injection port is much shorter than in splitless injection.

If the sensitivity of an instrument allows for split injection, then column capacity is not nearlythe issue it is for splitless injection. Figure 7 shows a 160ng-per-component standard injectedunder the same conditions as shown in Figure 6. A column with a thinner film can be usedbecause the concentration reaching the column is reduced by 20-fold. The analytical systemusing split injection will be able to handle higher concentrations of contaminants and possiblystay calibrated longer, but there will be a sacrifice in method detection limits (MDLs).Therefore, it is important to ensure that the MDLs specified in a particular method still can bemet if split injection is used.

18.5 16.0 16.5 17.0 17.5 18.0 18.5 19.0 19.5 20.0 20.5 min.

18 19 20 21 22 23 24 min.

Conditions for Fig. 4a30m, 0.25mm ID, 0.5µm Rtx®-5Sil MS(cat.# 12738)160ng splitless injection of CLPstandard; GC: HP/Agilent 6890 w/ 5973mass selective detector, scan range 35-550 AMU; Oven program: 40°C(hold 2min.) to 290°C @ 20°C/min. (hold 0min.) to 303°C @ 2°C/min. (hold 0 min.)to 330°C @ 6°C/min. (hold 1 min.);Carrier gas: He @ 1.0 mL/min. constantflow; Inj. temp.: 300°C; Det. temp.:280°C

Conditions for Fig. 4b30m, 0.25mm ID, 0.25µm Rtx®-5Sil MS(cat.# 12723)unknown concentration (>160ng)splitless injection of CLP standard;GC: HP/Agilent 6890 w/ 5973 massselective detector, scan range 35-550AMU; Oven program: 40°C (hold 2 min.)to 245°C @ 25°C/min. (hold 0 min.) to330°C @ 6°C/min. (hold 5 min.); Carriergas: He @ 1.0 mL/min. constant flow;Inj. temp.: 300°C; Det. temp.: 280°C

Page 12: Restek Column

12

Figure 5. A 30m, 0.25mm ID, 0.5µm Rtx®-5Sil MS column offers excellent resolution of 106 compounds listed in less than 25 minutes.

1. N-nitrosodimethylamine2. pyridine3. methyl methanesulfonate4. 2-fluorophenol5. ethyl methanesulfonate6. phenol-d67. phenol8. aniline9. bis(2-chloroethyl)ether

10. 2-chlorophenol11. 2-chlorophenol12. 1,3-dichlorobenzene13. 1,4-dichlorobenzene-d414. 1,4-dichlorobenzene15. benzyl alcohol16. 1,2-dichlorobenzene-d417. 1,2-dichlorobenzene18. 2-methylphenol19. bis(2-chloroisopropyl)ether20. 4-methylphenol/3-methylphenol21. N-nitroso-di-n-propylamine

22. acetophenone23. hexachloroethane24. nitrobenzene-d525. nitrobenzene26. isophorone27. 2,4-dimethylphenol28. 2-nitrophenol29. benzoic acid30. bis(2-chloroethoxy)methane31. 2,4-dichlorophenol32. 1,2,4-trichlorobenzene33. naphthalene-d834. naphthalene35. 2,6-dichlorophenol36. 4-chloroaniline37. hexachloropropene38. hexachlorobutadiene39 4-chloro-3-methylphenol40. isosafrole41. 2-methylnaphthalene42. 1-methylnaphthalene

43. hexachlorocyclopentadiene44. 1,2,4,5-tetrachlorobenzene45. 2,4,6-trichlorophenol46. 2,4,5-trichlorophenol47. 2-fluorobiphenyl48. safrole49. 2-chloronaphthalene50. 2-nitroaniline51. 1,4-naphthoquinone52. dimethylphthalate53. 1,3-dinitrobenzene54. 2,6-dinitrotoluene55. acenaphthylene56. 3-nitroaniline57. acenaphthene-d1058. acenaphthene59. 2,4-dinitrophenol60. 4-nitrophenol61. pentachlorobenzene62. 2,4-dinitrotoluene63. dibenzofuran

64. 2,3,4,6-tetrachlorophenol65. diethyl phthalate66. 4-chlorophenyl phenyl ether67. fluorene68. 4-nitroaniline69. 4,6-dinitro-2-methylphenol70. diphenylamine71. azobenzene72. 2,4,6-tribromophenol73. phenacetin74. 4-bromophenyl-phenyl ether75. hexachlorobenzene76. pentachlorophenol77. pentachloronitrobenzene78 dinoseb79. phenanthrene-d1080. phenanthrene81. anthracene82. di-n-butylphthalate83. 4-nitroquinoline-1-oxide84. isodrin

85. fluoranthene86. benzidine87. pyrene88. aromite89. p-terphenyl-d1490. chlorbenzilate91. butyl benzyl phthalate92. kepone93. bis(2-ethylhexyl)phthalate94. 3,3'-dichlorobenzidine95. benzo(a)anthracene96. chrysene-d1297. chrysene98. di-n-octyl phthalate99. benzo(b)fluoranthene

100. benzo(k)fluoranthene101. benzo(a)pyrene102. perylene-d12103. 3-methylcholanthrene104. indeno(1,2,3-cd)pyrene105. dibenz(a,h)anthracene106. benzo(g,h,i)perylene

1,2

3

4

5

6,7

10

34

47

58

6781

82

83

84

85

86

87,88

89

90 91

92

93

94

95,9697

98 99100

101

102 103

104,105 106

6,7

8

9

10,11

12

13,14

15

16,17

18

19

20 21,22

23 24

25 26

27,28

29,30

31

32

33

34

35,36

37

38

39

40

4142

44

43

45

46

47

48

49

50

5152

53

54

55

57

58

6059

61

62,63

64

6566

6768,69

70 7172

73

74 75

76

77

7879

8081

30m, 0.25mm ID, 0.5µmRtx®-5Sil MS (cat# 12738)

80ng splitless injection of CLPstandard; GC: HP/Agilent 6890w/ 5973 mass selective detector;Oven program: 40°C (hold 2min) to 290°C @ 20°C/min.(hold 0 min.) to 303°C @2°C/min. (hold 0 min.) to 330°C@ 6°C/min. (hold 1 min.);Carrier gas: He @ 1.0 mL/min.constant flow; Inj. temp.: 300°C;Det. temp.: 280C, scan range35-550 AMU

4 5 6 7 8 9 10 11 12 13 14 min.15 16 17 18 19 20 21 22 23 24

7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5 min.

19.0 19.5

Page 13: Restek Column

13

Figure 6. A 20ng split injection shows the extremely low bleed of the Rtx®-5Sil MS column.

1

2,34,5,6

1. 2-fluorophenol2. phenol-d63. phenol4. bis(2-chloroethyl)ether5. 2-chlorophenol6. 2-chlorophenol7. 1,3-dichlorobenzene8. 1,4-dichlorobenzene-d49. 1,4-dichlorobenzene

10. benzyl alcohol11. 1,2-dichlorobenzene-d412. 1,2-dichlorobenzene13. 2-methylphenol14. bis(2-chloroisopropyl)ether15. 4-methylphenol/3-methylphenol16. N-nitroso-di-n-propylamine17. hexachloroethane18. nitrobenzene-d519. nitrobenzene20. isophorone21. 2-nitrophenol22. 2,4-dimethylphenol23. benzoic acid24. bis(2-chloroethoxy)methane25. 2,4-dichlorophenol26. 1,2,4-trichlorobenzene27. naphthalene-d828. naphthalene29. 4-chloroaniline30. hexachlorobutadiene31. 4-chloro-3-methylphenol32. 2-methylnaphthalene33. hexachlorocyclopentadiene34. 2,4,6-trichlorophenol35. 2,4,5-trichlorophenol36. 2-fluorobiphenyl37. 2-chloronaphthalene38. 2-nitroaniline39. dimethylphthalate40. 2,6-dinitrotoluene

41. acenaphthylene42. acenaphthene-d1043. 3-nitroaniline44. acenaphthene45. 2,4-dinitrophenol46. 4-nitrophenol47. dibenzofuran48. 2,4-dinitrotoluene49. diethyl phthalate50. 4-chlorophenyl phenyl ether51. fluorene52. 4-nitroaniline53. 4,6-dinitro-2-methylphenol54. diphenylamine55. 2,4,6-tribromophenol56. 4-bromophenyl-phenyl ether57. hexachlorobenzene58. pentachlorophenol59. phenanthrene-d1060. phenanthrene61. anthracene62. carbazole63. di-n-butylphthalate64. fluoranthene65. pyrene66. p-terphenyl-d1467. butyl benzyl phthalate68. benzo(a)anthracene69. chrysene-d1270. chrysene71. bis(2-ethylhexyl)phthalate72. di-n-octyl phthalate73. benzo(b)fluoranthene74. benzo(k)fluoranthene75. benzo(a)pyrene76. perylene-d1277. indeno(1,2,3-cd)pyrene78. dibenz(a,h)anthracene79. benzo(ghi)perylene

30m, 0.25 mm ID, 0.25µm Rtx®-5Sil MS (cat.# 12723)20ng split injection of CLP standard; GC: HP/Agilent 6890 w/ 5973mass selective detector scan range 35-550 AMU; Oven program:40°C (hold 2 min.) to 245°C @ 25°C/min. (hold 0 min.) to 330°C

@ 6°C/min. (hold 5 min.); Carrier gas: He @ 1.0 mL/min.constant flow; Inj. temp.: 300°C; Det. temp.: 280°C

8,9

10,11,12

27,28

32

42,43

50,51

59,60

62

63 6465

66

67

68,69

70

71

72

737475

76

7778 79

2,35,6

4

7

8,9

10,11,12

13,1415,16

1718

19 20

21

2223,24

25

26

27

28

29

30

31

32

33

3534

36

37

38

39

40

41

42,43

44

4546

47

48

49

50,51

5253

54

55

56

57

58

59

60

61

62

63

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24

5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 min.

Peak List for Figures 6 & 7

Page 14: Restek Column

Figure 7. Analyzing semivolatile compounds in the split injection mode can improve peak shape and eliminate column overload.

2,3

4,5,6

7

8,9

10,11,12

13,14

15,16

17

27,28

29

30

31

32

33

35

3637

38

3940

4142,43

44

45

46

47

34

7273

74

75

76

7778 79

797877

76

75

747372

71

69,70

6867

666564

18

19 20

21

22

23,24 26

25

48

49

50,51

52,53

5455

56

57

58

59

60 61

6263

1

4,5,6

10,11,12

15,16 27,28

3236 41

44

50,51

56

57

30m, 0.25mm ID, 0.25µmRtx®-5Sil MS (cat.# 12723)

Sample: 160ng split injection of CLP standard;GC: HP/Agilent 6890 w/ 5973 mass selective

detector, scan range 35-550 AMU; Oven program:40°C(hold 2 min.) to 245°C @ 25°C/min. (hold 0min.) to 330°C @ 6°C/min. (hold 5 min.); Carriergas: He @ 1.0mL/min. constant flow; Inj. temp.:

300°C; Det. temp.: 280°C

Peak list on page 13

?Questions?Restek’s Technical Service

Team is always here to help.Call us at 800-356-1688 or

814-353-1300, ext. 4,or email us at

[email protected] (U.S.)or [email protected] (outside the U.S.)

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 min.

15.0 15.5 16.0 16.5 17.0 17.5 18.0 18.5 19.0 19.5 20.0 20.5 min.

5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 min.

Page 15: Restek Column

15

Reducing DiscriminationReduced response of the higher molecular weight semivolatile compounds can be caused bydiscrimination in the injection port. In extreme cases response for the last three PAH com-pounds may be lost completely at lower calibration levels. To reduce the effects of discrimina-tion in the injection port, we recommend using a drilled Uniliner® inlet liner. Because thecolumn seals into the taper at the bottom of the liner, there is reduced loss of high molecularweight compounds and improved response. The drilled Uniliner® inlet liner has a small holedrilled at the entrance that allows it to work with small diameter columns and ElectronicPressure Control (EPC) injection systems. When using the drilled Uniliner® liner (Figure 8),the response of the last three PAHs is significantly higher compared to the same analysis donewith a normal splitless sleeve (see Figure 5). The drilled Uniliner® is available for Agilent5890 and 6890 GCs (see page 19).

Figure 8. The Rtx®-5Sil MS combined with the Siltek™ drilled Uniliner® liner exhibits excellent peak shape and response forthe semivolatile compounds listed in US EPA Method 8270.

1. N-nitrosodimethylamine2. pyridine3. methyl methanesulfonate4. 2-fluorophenol5. ethyl methanesulfonate6. phenol-d67. phenol8. aniline9. bis(2-chloroethyl)ether

10. 2-chlorophenol11. 1,3-dichlorobenzene12. 1,4-dichlorobenzene-d413. 1,4-dichlorobenzene14. 1,2-dichlorobenzene15. benzyl alcohol16. 2-methylphenol17. bis(2-chloroisopropyl)ether18. acetophenone19. 4-methylphenol/3-methylphenol20. N-nitroso-di-n-propylamine21. hexachloroethane22. nitrobenzene-d523. nitrobenzene24. isophorone25. 2-nitrophenol26. 2,4-dimethylphenol

27. bis(2-chloroethoxy)methane28. benzoic acid29. 2,4-dichlorophenol30. 1,2,4-trichlorobenzene31. naphthalene-d832. naphthalene33. 2,6-dichlorophenol34. 4-chloroaniline35. hexachloropropene36. hexachlorobutadiene37. 4-chloro-3-methylphenol38. isosafrole39. 2-methylnaphthalene40. 1-methylnaphthalene41. hexachlorocyclopentadiene42. 1,2,4,5-tetrachlorobenzene43. 2,4,6-trichlorophenol44. 2,4,5-trichlorophenol45. 2-fluorobiphenyl46. safrole47. 2-chloronaphthalene48. 2-nitroaniline49. 1,4-naphthoquinone50. dimethylphthalate51. 1,3-dinitrobenzene52. 2,6-dinitrotoluene

53. acenaphthylene54. acenaphthene-d1055. 3-nitroaniline56. acenaphthene57. 2,4-dinitrophenol58. pentachlorobenzene59. 4-nitrophenol60. dibenzofuran61. 2,4-dinitrotoluene62. 2,3,4,6-tetrachlorophenol63. diethyl phthalate64. fluorene65. 4-chlorophenyl phenyl ether66. 4-nitroaniline67. 4,6-dinitro-2-methylphenol68. diphenylamine69. azobenzene70. 2,4,6-tribromophenol71. phenacetin72. 4-bromophenyl phenyl ether73. hexachlorobenzene74. pentachlorophenol75. pentachloronitrobenzene76. phenanthrene-d1077. dinoseb78. phenanthrene

79. anthracene80. di-n-butylphthalate81. 4-nitroquinoline-1-oxide82. isodrin83. fluoranthene84. benzidine85. pyrene86. p-terphenyl-d1487. aramite88. chlorbenzilate89. kepone90. butyl benzyl phthalate91. benzo(a)anthracene92. 3,3'-dichlorobenzidine93. chrysene-d1294. chrysene95. bis(2-ethylhexyl)phthalate96. di-n-octyl phthalate97. benzo(b)fluoranthene98. benzo(k)fluoranthene99. benzo(a)pyrene

100. perylene-d12101. 3-methylcholanthrene102. indeno(1,2,3-cd)pyrene103. dibenzo(a,h)anthracene104. benzo(g,h,i)perylene

30m, 0.25mm ID, 0.25µm Rtx®-5Sil MS (cat.# 12723)Conc.: 24µg/mL in methylene chloride(cat.#s: 31618, 31619, 31620, 31621, 31622, 31206,31062, 31063)Note: Internal standards at 8 ppm

Inj. vol.: 1µLInj type: splitlessHold time: 0.4 min.Inlet liner: drilled Uniliner® liner, Siltek™

deactivation (cat# 21054-214.1)Inj. temp.: 300°C

Carrier gas: helium (1mL/min. constant flow)Linear velocity: 34cm/sec.Oven temp.: 35°C (hold 2 min.) to 260°C @

20°C min. (hold 0 min.), to 330° @6°C/min. (hold 1 min.)

Det. type: MSTransfer line temp.: 280°CScan range: 35 to 550amuIonization: EIMode: full scan

GC_EV00576

Page 16: Restek Column

16

QuantitationBecause splitless injections suffer from irreproducibility, quantitation for semivolatilecompounds is by internal standard, using a single ion for each analyte. Internal standards atknown concentrations are used to correct for variances in the amount of material transferredto the column with different injections, and also to track MS sensitivity.

All sample analyte concentrations are calculated using response factors obtained from thecalibration curve. This method uses single ions (i.e., extracted ions) for each compound sothat chromatographic resolution of each compound is not necessary. It is acceptable forcompounds to co-elute, as long as they do not have any common ions used for quantitation.Typically, only isomers have similar spectra, so chromatographic resolution is required onlyfor these compounds.

Figure 9 shows the possibilities for calibration curves for this analysis. Curve A is the desiredresult, indicating a proportional response with increasing concentration. This implies thatthere is no detector saturation or reactivity for this compound. Curve B is indicative of acompound that undergoes a reaction, usually in the injection port or on the head of thecolumn. If a calibration curve like Curve B is observed, injection port or column maintenanceis required. Finally, Curve C shows high-end roll-off, indicating saturation. If a calibration

Figure 9. Calibration curves showing linear response, adsorption, and high-end roll-off.

resp

once

(are

a co

unts

)

concentration

CA

B

20000

40000

60000

80000

100000

120000

140000

160000

180000

200000

20 40 90 80 100 120 140 160

curve like Curve C is observed, select a column with higher capacity or reduce detectorsensitivity by lowering the multiplier voltage.

SummaryAlthough the analysis of semivolatile organic compounds is one of the more difficult testsperformed by environmental laboratories, using Restek’s Rtx®-5Sil MS or Rtx®-5MS columnsand following the tips presented in this guide can make it easier to perform. Correct samplepreparation, extract cleanup, injection technique, analytical columns, standards, and quantitationcan help minimize problems normally associated with semivolatile organic analyses. Whenproblems occur, use the most appropriate troubleshooting and maintenance procedures to quicklyoptimize your analytical system. When faced with difficulties in your semivolatile analysis,remember that the majority of problems occur in the sample preparation and cleanup step, or inthe GC injection port. If you still are having difficulties after reading through this guide, contactRestek’s Technical Service Team via email at [email protected] or via phone at800-356-1688 or 814-353-1300, ext. 4.

Page 17: Restek Column

Rtx®-5MSFused Silica (Crossbond® 5% diphenyl - 95%dimethyl polysiloxane) Stable to 360°C

Rtx®-5MS and Rtx®-5Sil MS ColumnsConventional capillary gas chromatography (GC) columns use liquid stationary phases, manyof which are crossbonded to yield a higher working temperature. Even with crossbonding,however, the liquid stationary phase will slowly elute. This elution of the stationary phase,also termed column bleed, is more detectable at higher temperatures and is typically observedas an increasing baseline that follows the oven temperature program. Depending on themethod of detection, column bleed may not be an issue for certain separations. If the capillarycolumn is connected to a sensitive detector like a mass spectrometer (MS), then column bleedcan cause a number of problems—specifically misidentification of analytes, loss of sensitiv-ity, and inaccurate quantitation.

The level of column bleed will affect the senstivity of any MS, especially ion trap instru-ments, which use automatic gain control. As the level of column bleed increases, so does thesignal from bleed ions in the mass spectra of analytes and unknowns. Also, sensitivity (ordetection limit) severely degrades. The contribution of bleed ions to the mass spectra canresult in misidentification of compounds, requiring laboratory personnel to subtract these ionsbefore performing library searches. Doing so can add considerable time to their analyses.Finally, if bleed ions contribute to the signal of the quantitation mass, quantitation of analytesand unknowns will be miscalculated. For these reasons, it is critical that analysts choose thelowest-bleed column designed for GC/MS applications.

Many manufacturers offer “MS” phases for applications requiring low bleed. In many cases,these represent nothing more than the reporting of the bleed signal when the column wastested for a single analysis at the manufacturer. Restek has developed true low-bleed MSphases. These columns exhibit a much lower column bleed than was previously available. TheRtx®-5MS column is a low-bleed, dimethyl/diphenyl polysiloxane phase. The Rtx®-5Sil MS isa low-bleed silarylene methyl/phenyl phase. The combination of Restek’s polymer chemistryand rigorous QA testing ensures that each MS column exceeds requirements of the mostsensitive mass spectrometers.

Rtx®-5Sil MSFused Silica (equivalent selectivity of Crossbond®

5% diphenyl/95% dimethyl polysiloxane)Stable to 360°C

ID df (µm) temp. limits 15-Meter 30-Meter 60-Meter0.25mm 0.10 -60 to 330/350°C 12605 12608 12611

0.25 -60 to 330/350°C 12620 12623 126260.50 -60 to 330/350°C 12635 12638 126411.00 -60 to 325/350°C 12650 12653

0.32mm 0.10 -60 to 330/350°C 12606 12609 126120.25 -60 to 330/350°C 12621 12624 126270.50 -60 to 330/350°C 12636 12639 126421.00 -60 to 325/350°C 12651 12654

0.53mm 0.50 -60 to 320/340°C 12637 126401.00 -60 to 320/340°C 12652 126551.50 -60 to 310/330°C 12667 12670

ID df (µm) temp. limits 15-Meter 30-Meter0.25mm 0.10 -60 to 330/350°C 12705 12708

0.25 -60 to 330/350°C 12720 127230.50 -60 to 330/350°C 12735 127381.00 -60 to 325/350°C 12750 12753

0.28mm 0.25 -60 to 330/350°C 12790 127930.50 -60 to 330/350°C 12791 127941.00 -60 to 325/350°C 12792 12795

0.32mm 0.10 -60 to 330/350°C 12706 127090.25 -60 to 330/350°C 12721 127240.50 -60 to 330/350°C 12736 127391.00 -60 to 325/350°C 12751 12754

0.53mm 0.50 -60 to 320/340°C 12737 127401.00 -60 to 320/340°C 12752 127551.50 -60 to 310/330°C 12767 12770

Page 18: Restek Column

18

For detailed information on typesof guard columns, their uses, and

a complete product listing,request Restek’s

Guard Column Fast Facts flyer(lit. cat.# 59319)

Intermediate-Polarity Deactivated Guard ColumnsNominal ID (mm) Nominal OD (mm) 1-Meter 5-Meter

0.15 0.363 ± 0.012 10101 10042

0.18 0.37 ± 0.04 10102 10046

0.25 0.37 ± 0.04 — 10043

0.28 0.37 ± 0.04 — 10003

0.32 0.45 ± 0.04 — 10044

0.45 0.69 ± 0.05 — 10005

0.53 0.69 ± 0.05 — 10045

formoreinfo

Innovative Integra-Guard™ ColumnsSome people swear by press-fit connectors, and others swear at them. For many analysts, theart of attaching a guard column to an analytical column is a mystery. Restek’s chemists havediscovered the solution to this mystery—the easiest, most reliable connection is no connectionat all! No guard column system is more permanent than one continuous length of tubingcontaining both the guard column and the analytical column.

Restek offers a wide variety of Integra-Guard™ capillary columns with a guaranteed leak-freeconnection! The guard column is tied separately from the analytical column, using high-temperature string. The transition area between the columns is the point at which the guardcolumn ends and the analytical column begins. The entire setup is suspended in our unique“crush-free” cage, which prevents the column from coming in contact with anything thatcould damage it.

Ordering is simple. Just add the appropriate suffix number and price to the analytical column’scatalog number and price. For example, a 30m, 0.25mm ID, 0.25µm Rtx®-5MS with a 5mIntegra-Guard™ column is cat.# 12623-124.

ID (mm) Length (m) Suffix #0.25 5 -124

10 -127

0.28 5 -243

10 -244

Integra-Guard™

built-in guardcolumn

Phases currently available asIntegra-Guard™ columns:

Rtx®-1 Rtx®-1701Rtx®-1MS Rtx®-VolatilesRtx®-5 Rtx®-20Rtx®-5MS Rtx®-35Rtx®-5Sil MS Rtx®-35MSXTI®-5 Rtx®-BAC 1 & 2Rtx®-1301 Stabilwax®

Rtx®-624

ID (mm) Length (m) Suffix #0.32 5 -125

10 -128

0.53 5 -126

10 -129

For analysts who prefer to attach a guard column to the analytical columnthemselves, Restek offers deactivated guard columns and Press-Tight® connectors.

Press-Tight® Connectors• Seals all common sizes (0.18 to 0.53mm ID, outside diameters from 0.3 to 0.75mm) of

fused silica tubing.• Connect guard columns to analytical columns, repair broken columns, or connect column

outlets to transfer lines.• Angled connectors are designed to approximate the curvature of a capillary column and reduce

strain on column-end connections.• Made from inert fused silica.

Universal Angled Press-Tight® Connectors:cat.# 20446 (5-pk.); cat.# 20447 (25-pk.); cat.# 20448 (100-pk.)

Universal Press-Tight® Connectors:cat.# 20400 (5-pk.); cat.# 20401 (25-pk.); cat.# 20402 (100-pk.)

Deactivated Universal Press-Tight® Connectors:cat.# 20429 (5-pk.); cat.# 20430 (25-pk.); cat.# 20431 (100-pk.)

Universal “Y” Press-Tight® Connectors:cat.# 20405 (ea.); cat.# 20406 (3-pk.)

Universal Angled “Y” Press-Tight® Connectors:cat.# 20403 (ea.); cat.# 20404 (3-pk.)

Page 19: Restek Column

19

For Varian GCs

Splitless Liners for ID*/OD & cat.# Similar toAgilent/HP & Finnigan GCs Benefits/Uses: Length (mm) ea. 5-pk. 25-pk. Agilent part #

trace samples >2µL 4.0 ID 20772 20773 20774 —4mm Splitless 6.5 OD x 78.5

trace samples >2µL 4.0 ID 22400 22401 22402 19251-605404mm Splitless w/ FS Wool 6.5 OD x 78.5

trace samples >2µL 4.0 ID 20912 20913 — —4mm Splitless (quartz) 6.5 OD x 78.5

trace samples >2µL 4.0 ID 22403 22404 — 18740-802204mm Splitless (quartz) w/ FS Wool 6.5 OD x 78.5 5181-8818

trace samples <2µL 2.0 ID 20795 20796 20797 —Gooseneck Splitless (2mm) 6.5 OD x 78.5

trace samples >2µL 4.0 ID 20798 20799 20800 5181-3316Gooseneck Splitless (4mm) 6.5 OD x 78.5

trace samples >2µL 4.0 ID 22405 22406 22407 5062-3587 Gooseneck Splitless (4mm) w/ FS Wool 6.5 OD x 78.5

trace, active samples >2µL 4.0 ID 20784 20785 20786 5181-3315Double Gooseneck Splitless (4mm) 6.5 OD x 78.5

trace, active, dirty 2.0 ID 20907 20908 — —Cyclo Double Gooseneck (2mm) samples <2µL 6.5 OD x 78.5

trace, active, dirty 4.0 ID 20895 20896 20997 —Cyclo Double Gooseneck (4mm) samples >2µL 6.5 OD x 78.5

allows direct injection when 4.0 ID 21054 21055 — —Drilled Uniliner® (4mm) using EPC-equipped GC 6.3 OD x 78.5

allows direct injection when 4.0 ID 21054-214.1 21055-214.5 — —Siltek™ Drilled Uniliner® (4mm) using EPC-equipped GC 6.3 OD x 78.5C

OL

UM

NI

NS

TA

LL

ST

HI

SE

ND

Inlet LinersFor Agilent/HP & Finnigan GCs

Splitless Liners for ID**/OD & cat.# Similar toVarian 1075/1077GCs Benefits/Uses: Length (mm) ea. 5-pk. 25-pk. Varian Part #

trace samples<2µL 2.0 ID 20721 20722 20723 01-900109-052mm Splitless 6.3 OD x 74

trace samples>2µL 4.0 ID 20904 20905 20906 01-900109-054mm Splitless 6.3 OD x 74

trace, active samples 4.0 ID 20847 20848 20849 —Double Gooseneck up to 4µL 6.3 OD x 74

trace, dirty, active 4.0 ID 20897 20898 — —Cyclo Double Gooseneck samples up to 4µL 6.3 OD x 74

1078/1079 Liners ID**/OD & cat.# Similar tofor Varian GCs Benefits/Uses: length (mm) ea. 5-pk. 25-pk. Varian Part #

trace samples <2µL 2.0 ID 21711 21712 — 03-918466-001078/1079 Splitless 5.0 OD x 54C

OL

UM

N I

NS

TA

LL

S T

HIS

EN

D

*Nominal ID at syringe needle expulsion point.

Page 20: Restek Column

20

Splitless Liners for ID**/OD & cat.# Similar toPerkinElmer GCs Benefits/Uses: Length (mm) ea. 5-pk. 25-pk. PE Part #

trace samples 2.0 ID 20829 20830 20831 N6101372Auto SYS Splitless w/Wool (2mm ID)* 6.2 OD x 92.1

trace, active samples 3.5 ID 20853 20854 — —Auto SYS Double Gooseneck up to 4µL 6.2 OD x 92.1

trace, dirty, active samples 3.5 ID 20899 20900 — —Auto SYS Cyclo Double Gooseneck up to 4µL 6.2 OD x 92.1

most common 2.0 ID 21717 21718 — N612-1004Auto SYS XL Split/Splitless analyses 4.0 OD x 86.2

Splitless Liners for ID**/OD & cat.# Similar to5000-6000 Series GCs Benefits/Uses: Length (mm) ea. 5-pk. 25-pk. TO Part #

trace samples 4.0 ID 20814 20815 20816 —Splitless (4mm ID) 5.5 OD x 79.5

Splitless Liners for 8000 ID**/OD & cat.# Similar to& TRACE™ Series GCs Benefits/Uses: Length (mm) ea. 5-pk. 25-pk. TO Part #

Splitless Liners for ID**/OD & cat.# Similar toShimadzu GCs Benefits/Uses: Length (mm) ea. 5-pk. 25-pk. Shimadzu Part #

trace samples 3.5 ID 20955 20956 20957 221-0914594mm Splitless with Wool* 5.0 OD x 94

reduces backflash and 3.5 ID 20958 20959 20960 —94mm Double Gooseneck catalytic decomposition 5.0 OD x 94

reduces backflash, also 3.5 ID 20961 20962 20963 221-41599-0094mm Single Gooseneck operates in DI mode 5.0 OD x 94

CO

LU

MN

IN

ST

AL

LS

TH

IS E

ND

trace samples 3.0 ID 20942 20943 20944 453 20032Splitless (3mm ID) 8.0 OD x 105

trace samples 5.0 ID 20945 20946 20947 453 20033Splitless (5mm ID) 8.0 OD x 105

trace, active samples 4.0 ID 20952 20953 — —Double Gooseneck up to 4µL 8.0 OD x 105

Inlet LinersFor Shimadzu GCs

For PerkinElmer GCs

For Thermo Orion GCs

*Liner is packed with fused silica wool. To order glass wool instead, add the suffix “–202” to the liner’s catalog number.**Nominal ID at syringe needle expulsion point.

CO

LU

MN

IN

ST

AL

LS

T

HIS

E

ND

O-RingsViton®

Viton® o-rings are universal. One size fits both split (6.3mm ID) and splitless (6.5mm ID) sleeves.

Max. temp. Similar to Agilent Part # cat.# Qty.Viton® (fluorocarbon) 350°C 5180-4182 20377 25-pk.

GraphiteGraphite o-rings have excellent thermal stability and can be used at injection port temperatures up to 450°C!

Similar to Agilent Part # 10-pk. 50-pk.6.35mm ID for split liners 5180-4168 20296 20297

6.5mm ID for splitless liners 5180-4173 20298 20299

Page 21: Restek Column

21

Deactivated Fused Silica Wool• Ensure uniform vaporization in split or splitless liners.• Prolong column life by trapping septum particles.• Recommended for autosamplers with fast injection rates.• Inertness tested for endrin breakdown.cat.# 20790, (10 grams)

Septum Diameter 25-pk. 50-pk. 100-pk.5mm (3/16") 20351 20352 203536mm (1/4") 20355 20356 203577mm 20381 20382 203838mm 20370 20371 —9.5mm (3/8") 20359 20360 2036110mm 20378 20379 2038011mm (7/16") 20363 20364 2036511.5mm 22385 22386 2238712.5mm (1/2") 20367 20368 2036917mm 20384 20385 20386Shimadzu Plug 20372 20373 20374

Thermolite® Septa• Each batch tested on FIDs, ECDs, & MSDs to ensure lowest bleed.• Excellent puncturability.• Preconditioned and ready to use.• Do not adhere to hot metal surfaces.• Usable to 340°C inlet temperatures.• Packaged in non-contaminating tins.

Call our literature hotlineat 800-356-1688

or 814-353-1300, ext. 5,or your local Restek

representative forRestek’s 20-page bulletin,

A Guide to MinimizingSepta Problems

(lit. cat.# 59886).

guidefree

Replacement Inlet Seals• Special grade of stainless steel deforms easily, ensuring a completely leak-free seal.• Available in stainless steel, gold-plated, and Silcosteel®-treated.• Cross-Disk ideal for high-flow split applications on EPC-equipped GCs.• Shipped with washers.

*0.8mm ID stainless steel inlet seal is equivalent toAgilent part #18740-20880.**0.8mm ID gold-plated inlet seal is equivalent toAgilent part #18740-20885.

Single-Column Installation,Opening Size 0.8mm ID

Stainless Steel Inlet Seal*

21315, 2-pk. 21316, 10-pk.

Gold-Plated Inlet Seal**

21317, 2-pk. 21318, 10-pk.

Silcosteel® Inlet Seal

21319, 2-pk. 21320, 10-pk.

For Agilent 5890/6890/6850Split/Splitless Injection Ports Cross-Disk, Opening Size 0.8mm ID

Gold-Plated Inlet Seal

20477, 2-pk. 20476, 10-pk.

Silcosteel® Inlet Seal

20475, 2-pk. 20474, 10-pk.

Cross-Disk, Opening Size 1.2mm ID

Gold-Plated Inlet Seal

21009, 2-pk. 21010, 10-pk.

Silcosteel® Inlet Seal

21011, 2-pk. 21012, 10-pk.

Cross-Disk for Agilent GCs†

†Similar to Agilent part #5182-9652.

Request the handy,pocket-sized, InletSupplies Guide(lit. cat.# 59893A).

guidefree

Page 22: Restek Column

22

Capillary Ferrules (for 1/16" compression-type fittings)

Ferrule Fits Column Vespel®/ID (mm) ID (mm) Qty. Graphite Graphite

0.4 0.25 50-pk. 20227 20229

0.4 0.25 10-pk. 20200 20211

0.5 0.32 10-pk. 20201 20212

0.5 0.32 50-pk. 20228 20231

0.6 0.28 10-pk. — 20232

0.8 0.53 10-pk. 20202 20213

0.8 0.53 50-pk. 20224 20230

Ferrules

Compact Ferrules for Agilent GCs

Ferrule Fits Column Vespel®/ID (mm) ID (mm) Qty. Graphite Graphite

0.4 0.25 10-pk. 20250 20238

0.4 0.25 50-pk. 20251 20239

0.5 0.32 10-pk. 21007 20248

0.5 0.32 50-pk. 21008 20249

0.8 0.53 10-pk. 20252 20263

0.8 0.53 50-pk. 20253 20264

Encapsulated Ferrules• Will not deform and stick in fittings.• Reusable.• For 1/16" compression fittings.

Ferrule ID Fits column ID cat.#/10-pk.0.4mm 0.25mm 21036

0.5mm 0.32mm 21037

0.8mm 0.53mm 21038

EZ-Vent™ 2000• Change GC/MS columns in minutes without venting.• Silcosteel® treated for greater inertness.• Deactivated transfer line minimizes bleed into the source.• Stainless steel body and high-temperature polyimide

ferrules minimize leaks at the problematic transfer line fitting.• Less expensive than other “no-vent” fittings.• 100µm transfer line throttles vacuum and prevents column pump down.• Available for Agilent GCs with 5971/5972 or 5973 MS and Varian 3400, 3600, or 3800

GCs with Saturn 2000 MS.• Precision-machined orifice.

KitsEZ-Vent™ 2000 for Agilent GCs with 5971/5972 or 5973 MS

Includes EZ-Vent™ 2000, 1/16" SS nut, 0.4mm ID ferrules for connecting capillary column,0.4mm ID ferrules for connecting transfer line, 100µm deactivated transfer line (3 ft.), andEZ-Vent™ column plug; cat.# 21013, (kit)

EZ-Vent™ 2000 for Varian Saturn 2000 MS systems with 3400, 3600, or 3800 GCsIncludes EZ-Vent™ 2000, 1/16" SS nut, 0.4mm ferrules for connecting capillary column,0.4mm ID ferrules for connecting transfer line, 100µm deactivated transfer line (3 ft.), andEZ-Vent™ column plug; cat.# 21014, (kit)

great

idea!EZ-Vent™ 2000 for Agilent GCs

EZ-Vent™ 2000 for Varian GCs

EZ-Vent™ 2000 ferrules

Page 23: Restek Column

23

For Agilent 5890 GCsDescription cat.#, (ea.)

Replacement Weldment (Similar to Agilent part# 19251-60575) 20265

Replacement Shell Weldment (Similar to Agilent part# 19251-80570) 20266

Silcosteel® Weldment 20267

Silcosteel® Shell Weldment 20268

Direct Replacement Split/Splitless Injection Ports for Agilent GCs

Would you like better performance from your injector? Restek’s Silcosteel®-coated split/splitless injector is a direct replacement for Agilent 5890 and 6890/6850 GCs. The injector

version available

®

For Agilent 6890/6850 GCsDescription cat.#, (ea.)

Replacement Weldment for Agilent 6890/6850 GCs with EPC 22674

Replacement Weldment for Agilent 6890/6850 GCs with manual flow 20265

Replacement Shell Weldment for Agilent 6890/6850 GCs 22673

Weldment for Agilent 5890 GCs

MSD Source NutThe nut bore has been changed from 0.8mm to 1.2mm to permit easy removal of ferrules witha standard tapered-needle file (cat.# 20106). The nuts still match the manufacturer’s originalpart specifications and are made of brass to prevent thread-stripping on the transfer line.(Similar to Agilent part #05988-20066.)(Detector) MSD Source Nut: cat.# 20643, (2-pk.)

Agilent’s MSD interfacerequires a butt-seal at thebase of a Vespel® ferrule,

which is prone to leakage.Restek’s version uses a

standard ferrule design thatsimultaneously seals the

fitting and capillary tubingwith compressive forces.

MSD Conversion Fitting—Improved• Uses a flat, soft aluminum sealing ring to deform and butt-seal against the MSD interface

(see figure below).• A standard Vespel® ferrule seals the column and 1/16-inch stainless steel nut.• Fitting is constructed of nickel-plated brass for longevity and softness.• Can use any standard Vespel® or Vespel®/graphite 1/16-inch ferrule.• Includes a 1/16-inch stainless steel nut and two replacement sealing rings. Order ferrules

separately.MSD Conversion Fitting: cat.# 21314, (ea.)MSD Conversion Fitting Replacement Ring Seal: cat.# 21313, (2-pk.)

Restek MSD Conversion Fitting

only columnseals at taper

butt-sealwith ferrule crunch washer

forms leak-freeseal—easier to

remove

ferrule sealsagainst

both column andfitting

shoulderstrength

increased

Original Agilent Design

SOURCE

SOURCE

is manufactured from high-quality stainless steel andmeets or exceeds Agilent original equipment specifica-tions. Silcosteel® passivates the metal surface to ensurean inert pathway for the sample, delivering increasedperformance.

Shell weldment for Agilent5890 GCs

Weldment and shellweldment for Agilent

6890/6850 GCs

✓ check it out

Page 24: Restek Column

24

Internal Standard Mixtures

SV Internal Standard Mixacenaphthene-d10 naphthalene-d8crysene-d12 perylene-d121,4-dichlorobenzene-d4 phenanthrene-d10

4,000µg/mL each in methylene chloride, 1mL/ampul

Each 5-pk. 10-pk.31006 31006-510

w/data pack 31006-500 31006-520 31106

2,000µg/mL each in methylene chloride, 1mL/ampul

Each 5-pk. 10-pk.31206 31206-510

w/data pack 31206-500 31206-520 31306

Surrogate Mixtures

B/N Surrogate Mix (4/89 SOW)2-fluorobiphenyl p-terphenyl-d14nitrobenzene-d5

1,000µg/mL each in methylene chloride, 1mL/ampul

Each 5-pk. 10-pk.31024 31024-510

w/data pack 31024-500 31024-520 31124

5,000µg/mL each in methylene chloride, 1mL/ampul

Each 5-pk. 10-pk.31062 31062-510

w/data pack 31062-500 31062-520 31162

5,000µg/mL each in methylene chloride, 5mL/ampul

Each 5-pk. 10-pk.31086 31086-510

w/data pack 31086-500 31086-520 31186

Acid Surrogate Mix (4/89 SOW)2-fluorophenol 2,4,6-tribromophenolphenol-d6

2,000µg/mL each in methylene chloride, 1mL/ampul

Each 5-pk. 10-pk.31025 31025-510

w/data pack 31025-500 31025-520 31125

10,000µg/mL each in methylene chloride, 1mL/ampul

Each 5-pk. 10-pk.31063 31063-510

w/data pack 31063-500 31063-520 31163

10,000µg/mL each in methylene chloride, 5mL/ampul

Each 5-pk. 10-pk.31087 31087-510

w/data pack 31087-500 31087-520 31187

US EPA Methods 8270C & 8270D Analytical Reference Materials

US EPA Method 8270D outlines theanalysis of semivolatile organic pollutants

in solid waste, soil, water, and air matrices,using GC/MS. Update IVA of the thirdedition of SW-846—Test Methods for

Evaluating Solid Waste, Physical/ChemicalMethods—includes EPA Method 8270D, in

which there were no major revisions fromEPA Method 8270C.

Matrix Spiking Mixtures

B/N Matrix Spike Mixacenaphthene N-nitroso-di-n-propylamine1,4-dichlorobenzene pyrene2,4-dinitrotoluene 1,2,4-trichlorobenzene

1,000µg/mL each in methylene chloride, 1mL/ampul

Each 5-pk. 10-pk.31004 31004-510

w/data pack 31004-500 31004-520 31104

5,000µg/mL each in methylene chloride, 1mL/ampul

Each 5-pk. 10-pk.31074 31074-510

w/data pack 31074-500 31074-520 31174

5,000µg/mL each in methylene chloride, 5mL/ampul

Each 5-pk. 10-pk.31084 31084-510

w/data pack 31084-500 31084-520 31184

GC/MS Tuning Mixture

GC/MS Tuning Mixturebenzidine DFTPP4,4'-DDT pentachlorophenol

1,000µg/mL each in methylene chloride, 1mL/ampul

Each 5-pk. 10-pk.31615 31615-510

w/data pack 31615-500 31615-520 31715

Aramite Mix2,000ppm each in hexane, 1mL/ampul

Each 5-pk. 10-pk.31624 31624-510

w/data pack 31624-500 31624-520 31724

Method 8270 Calibration Kits

8270 Calibration Kit31618: 8270 Calibration Mix #131619: 8270 Calibration Mix #231620: 8270 Calibration Mix #331621: 8270 Calibration Mix #431622: 8270 Calibration Mix #5

Contains 1mL each of these mixtures.

Kit Kit w/Data Pack31626 31626-500

8270/Appendix IX Calibration Kit31618: 8270 Calibration Mix #131619: 8270 Calibration Mix #231620: 8270 Calibration Mix #331621: 8270 Calibration Mix #431622: 8270 Calibration Mix #531623: 8270 Calibration Mix #631625: Appendix IX Mix #1

Contains 1mL each of these mixtures.

Kit Kit w/Data Pack31627 31627-500

kit

kit

Acid Matrix Spike Mix4-chloro-3-methylphenol pentachlorophenol2-chlorophenol phenol4-nitrophenol

2,000µg/mL each in methylene chloride, 1mL/ampul

Each 5-pk. 10-pk.31014 31014-510

w/data pack 31014-500 31014-520 31114

10,000µg/mL each in methylene chloride, 1mL/ampul

Each 5-pk. 10-pk.31061 31061-510

w/data pack 31061-500 31061-520 31161

10,000µg/mL each in methylene chloride, 5mL/ampul

Each 5-pk. 10-pk.31071 31071-510

w/data pack 31071-500 31071-520 31171

Page 25: Restek Column

25

Calibration Check CompoundMixtures

8270 B/N Calibration Check Mixacenaphthene diphenylaminebenzo(a)pyrene fluoranthene1,4-dichlorobenzene hexachlorobutadienedi-n-octyl phthalate

2,000µg/mL each in methylene chloride, 1mL/ampul

Each 5-pk. 10-pk.31616 31616-510

w/data pack 31616-500 31616-520 31716

8270 Acid Calibration Check Mix4-chloro-3-methylphenol pentachlorophenol2,4-dichlorophenol phenol2-nitrophenol 2,4,6-trichlorophenol

2,000µg/mL each in methylene chloride, 1mL/ampul

Each 5-pk. 10-pk.31617 31617-510

w/data pack 31617-500 31617-520 31717

Calibration Mixtures

8270 Calibration Mix #1benzoic acid 3-methylphenol4-chloro-3-methylphenol 4-methylphenol2-chlorophenol 2-nitrophenol2,4-dichlorophenol 4-nitrophenol2,6-dichlorophenol pentachlorophenol2,4-dimethylphenol phenol4,6-dinitro-2-methylphenol 2,3,4,6-tetrachlorophenol2,4-dinitrophenol 2,4,5-trichlorophenoldinoseb 2,4,6-trichlorophenol2-methylphenol

2,000µg/mL each in methylene chloride, 1mL/ampul

Each 5-pk. 10-pk.31618 31618-510

w/data pack 31618-500 31618-520 31718

8270 Calibration Mix #2aniline 3-nitroanilinebenzidine 4-nitroaniline4-chloroaniline N-nitrosodimethylamine3,3'-dichlorobenzidine N-nitrosodi-n-propylaminediphenylamine pyridine2-nitroaniline

2,000µg/mL each in methylene chloride, 1mL/ampul

Each 5-pk. 10-pk.31619 31619-510

w/data pack 31619-500 31619-520 31719

US EPA Methods 8270C & 8270D Analytical Reference Materials

Calibration Mixtures

8270 Calibration Mix #3aramite hexachlorobenzenebis (2-chloroethyl) ether hexachlorobutadienebis (2-chloroethoxy) methane hexachloro-

cyclopentadienebis (2-chloroisopropyl) ether hexachloroethane4-bromophenyl phenyl ether hexachloropropenechlorobenzilate isodrin2-chloronaphthalene kepone4-chlorophenyl phenyl ether pentachlorobenzene1,2-dichlorobenzene pentachloronitrobenzene1,3-dichlorobenzene 1,2,4,5-tetrachlorobenzene1,4-dichlorobenzene 1,2,4-trichlorobenzene1,3-dinitrobenzene

2,000µg/mL each in methylene chloride, 1mL/ampul

Each 5-pk. 10-pk.31620 31620-510

w/data pack 31620-500 31620-520 31720

8270 Calibration Mix #4acetophenone 2,6-dinitrotolueneazobenzene ethyl methanesulfonatebenzyl alcohol isophoronebis (2-ethylhexyl) phthalate isosafrole (cis & trans)butyl benzyl phthalate methyl methanesulfonatedibenzofuran 1,4-naphthoquinonediethyl phthalate nitrobenzenedimethyl phthalate 4-nitroquinoline-1-oxidedi-n-butyl phthalate phenacetindi-n-octyl phthalate safrole2,4-dinitrotoluene

2,000µg/mL each in methylene chloride, 1mL/ampul

Each 5-pk. 10-pk.31621 31621-510

w/data pack 31621-500 31621-520 31721

8270 Calibration Mix #5acenaphthene fluorantheneacenaphthylene fluoreneanthracene ideno(1,2,3-cd)pyrenebenzo(a)anthracene 3-methylcholanthrenebenzo(a)pyrene 1-methylnaphthalenebenzo(b)fluoranthene 2-methylnaphthalenebenzo(ghi)perylene naphthalenebenzo(k)fluoranthene phenanthrenechrysene pyrenedibenz(a,h)anthracene

2,000µg/mL each in methylene chloride, 1mL/ampul

Each 5-pk. 10-pk.31622 31622-510

w/data pack 31622-500 31622-520 31722

8270 Calibration Mix #6diallate (cis & trans) parathiondimethoate phoratedisulfoton pronamidefamphur thionazinemethyl parathion 0,0,0-triethylphosphorothioate

2,000µg/mL each in methylene chloride, 1mL/ampul

Each 5-pk. 10-pk.31623 31623-510

w/data pack 31623-500 31623-520 31723

Organochlorine Pesticide Mix AB #1aldrin endosulfan IIα-BHC endosulfan sulfateα-chlordane endrinβ-BHC endrin aldehyde4,4'-DDD endrin ketone4,4'-DDE γ-BHC (lindane)4,4'-DDT γ-chlordaneδ-BHC heptachlordieldrin heptachlor epoxide (B)endosulfan I methoxychlor

200µg/mL each in hexane/toluene (1:1), 1mL/ampul

Each 5-pk. 10-pk.32291 32291-510

w/data pack 32291-500 32291-520 32391

Appendix IX Mix #12-acetylaminofluorene N-nitrosodiethylamine4-aminobiphenyl N-nitrosomethylethylaminep-dimethylaminoazobenzene N-nitrosomorpholine3,3'-dimethylbenzidine N-nitrosopiperidineα,α,-dimethylphenethylamine N-nitrosopyrrolidine (free base) 1,4-phenylenediaminemethapyrilene (free base) 2-picoline1-naphthylamine o-toluidine2-naphthylamine5-nitro-o-toluidineN-nitrosodibutylamine

2,000µg/mL each in methylene chloride, 1mL/ampul

Each 5-pk. 10-pk.31625 31625-510

w/data pack 31625-500 31625-520 31725

Calibration Mixtures

Page 26: Restek Column

EPA CLP—Semivolatiles Calibration Mixtures

04.1 SOW, 04.2 OSWRestek chemists carefully reviewed the 04.2 Statement of Work and determined that theidentical products listed in 04.1 will also be required for the 04.2 revision. The products listedhere are a result of this work.

CLP 04.1 B/N MegaMix™

Note: This product is provided as a two ampul set:

CLP 04.1 B/N MegaMix™ Mix Aacenaphthene di-n-octyl phthalateacenaphthylene dibenz(a,h)anthraceneacetophenone dibenzofurananthracene 3,3'-dichlorobenzidineatrazine diethyl phthalatebenzo(a)anthracene dimethyl phthalatebenzaldehyde 2,4-dinitrotoluenebenzo(a)pyrene 2,6-dinitrotoluenebenzo(b)fluoranthene fluoranthenebenzo(k)fluoranthene fluorenebenzo(ghi)perylene hexachlorobenzene1,1'-biphenyl hexachlorobutadienebis(2-chloroethoxy)methanehexachlorocyclopentadienebis(2-chloroethyl)ether hexachloroethanebis-(2-chloroisopropyl)ether ideno(1,2,3-cd)pyrenebis(2-ethylhexyl)phthalate isophorone4-bromophenyl phenyl ether 2-methylnaphthalenebutyl benzyl phthalate naphthalenecaprolactam nitrobenzenecarbazole n-nitrosodi-n-propylamine2-chloronaphthalene n-nitrosodiphenylamine4-chlorophenyl phenyl ether phenanthrenechrysene pyrenedi-n-butyl phthalate

1,000µg/mL each in methylene chloride/benzene (75:25)

CLP 04.1 B/N MegaMix™ Mix B4-chloroaniline 3-nitroaniline2-nitroaniline 4-nitroaniline

1,000µg/mL each in methylene chloride

Each 5-pk. 10-pk.31495 31495-510 —

w/data pack 31495-500 31495-520 31595

CLP 04.1 Phenols Calibration Mix4-chloro-3-methylphenol 2-methylphenol2-chlorophenol 4-methylphenol4-nitrophenol 2-nitrophenol2,4-dichlorophenol pentachlorophenol2,4-dimethylphenol phenol2,4-dinitrophenol 2,4,5-trichlorophenol2-methyl-4,6-dinitrophenol 2,4,6-trichlorophenol

2,000µg/mL each in methylene chloride, 1mL/ampul

Each 5-pk. 10-pk.31494 31494-510 —

w/data pack 31494-500 31494-520 31594

CLP GPC Calibration Mixbis(2-ethylhexyl)phthalate 10mg/mL

052lio nroc0.2rolhcyxohtem2.0enelyrep8.0ruflus

In methylene chloride, 1mL/ampul

1mL/ampul Each 5-pk. 10-pk.32019 32019-510 32119

5mL/ampul Each 5-pk. 10-pk.32023 32023-510 32123

CLP GPC Calibration Mix

Qualitative mixture useful for determining GPCdump/collect times. Data packs are not available.The compounds are dissolved in methylenechloride at the concentrations listed.

Revised GPC Calibration Mixbis(2-ethylhexyl)phthalate 5mg/mL

052lio nroc0.1rolhcyxohtem2.0enelyrep8.0ruflus

In methylene chloride, 1mL/ampul

1mL/ampul Each 5-pk. 10-pk.32041 32041-510 32141

5mL/ampul Each 5-pk. 10-pk.32042 32042-510 32142

RestekTip

CLP OLM 04.1, 04.2Semivolatile Dilution

Benzaldehyde and atrazine will reactquickly and directly with the methanolstabilizer used in most brands andgrades of methylene chloride. Thisreaction will prevent you fromobtaining stable, working-levelcalibration standards. Therefore, Restekhas prepared the CLP OLM 04.1Semivolatile B/N Mega- Mix™ frommethylene chloride that is stabilizedwith amylene and is completely free ofmethanol. Restek strongly recommendsscreening the methylene chloride youuse to dilute these mixtures to confirmthat it is free of methanol.

CLP OLM 04.1 SV Kit #1

31000: SV Screening Mix31001:SV Tuning Mix31493:CLP 04.1 BNA Surrogate Mix31492:CLP 04.1 B/N Matrix Spike Mix31005:Acid Matrix Spike Mix31006:SV Internal Standard Mix31494:CLP 04.1 Phenols Calibration Mix31495:CLP 04.1 B/N MegaMix™

31012:SV Calibration Mix #6 (pesticides)

Contains 1mL each of these mixtures.

Kit Kit w/Data Pack31603 31603-500

CLP OLM 04.1 SV Kit #2

31494:CLP 04.1 Phenols Calibration Mix31495:CLP 04.1 B/N MegaMix™

31012:SV Calibration Mix #6 (pesticides)

Contains 1mL each of these mixtures.

Kit Kit w/Data Pack31604 31604-500

CLP OLM 04.1 SV Kit #3

31494:CLP 04.1 Phenols Calibration Mix31495:CLP 04.1 B/N MegaMix™

Contains 1mL each of these mixtures.

Kit Kit w/Data Pack31605 31605-500

kit

kit

kit�

Page 27: Restek Column

27

CLP Semivolatile Calibration Kit #1(with pesticides)

31007: SV Calibration Mix #1 (anilines)31008: SV Calibration Mix #2 (phenols)31009: SV Calibration Mix #3 (base neutrals)31010: SV Calibration Mix #4 (base neutrals)31011: SV Calibration Mix #5 (PAHs)31012: SV Calibration Mix #6 (pesticides)31013: SV Calibration Mix #7 (dichlorobenzenes)31026: 3,3'-dichlorobenzidine

Contains 1mL each of these mixtures.

Kit Kit w/Data Pack31461 31461-500

CLP Semivolatile Calibration Kit #2(without pesticides)

31007: SV Calibration Mix #1 (anilines)31008: SV Calibration Mix #2 (phenols)31009: SV Calibration Mix #3 (base neutrals)31010: SV Calibration Mix #4 (base neutrals)31011: SV Calibration Mix #5 (PAHs)31013: SV Calibration Mix #7 (dichlorobenzenes)31026: 3,3'-dichlorobenzidine

Contains 1mL each of these mixtures.

Kit Kit w/Data Pack31462 31462-500

Semivolatile Calibration Kit #3(with benzidine)

31007: SV Calibration Mix #1 (anilines)31008: SV Calibration Mix #2 (phenols)31009: SV Calibration Mix #3 (base neutrals)31010: SV Calibration Mix #4 (base neutrals)31011: SV Calibration Mix #5 (PAHs)31013: SV Calibration Mix #7 (dichlorobenzenes)31030: 605 Benzidines Calibration Mix

(benzidine & 3,3'-dichlorobenzidine)

Contains 1mL each of these mixtures.

Kit Kit w/Data Pack31463 31463-500

Semivolatile Organics Kit (3/90 SOW)31000: SV Screening Mix31001: SV Tuning Compound31002: B/N Surrogate Std. Mix (3/90 SOW)31003: Acid Surrogate Std. Mix (3/90 SOW)31004: B/N Matrix Spike Mix31005: Acid Matrix Spike Mix31006: SV Internal Standard Mix31007: SV Calibration Mix #131008: SV Calibration Mix #231009: SV Calibration Mix #331010: SV Calibration Mix #431011: SV Calibration Mix #531012: SV Calibration Mix #631013: SV Calibration Mix #731026: 3,3'-dichlorobenzidine

Contains 1mL each of these mixtures.

Kit Kit w/Data Pack31051 31151

kit

kit

kit

kit

SV Calibration Mix #1benzyl alcohol 3-nitroaniline4-chloroaniline 4-nitroaniline2-nitroaniline

2,000µg/mL each in CH2Cl

2, 1mL/ampul

Each 5-pk. 10-pk.31007 31007-510

w/data pack 31007-500 31007-520 31107

SV Calibration Mix #2benzoic acid 4-methylphenol4-chloro-3-methylphenol 2-nitrophenol2-chlorophenol 4-nitrophenol2,4-dichlorophenol pentachlorophenol2,4-dimethylphenol phenol2,4-dinitrophenol 2,4,5-trichlorophenol2-methyl-4,6-dinitrophenol 2,4,6-trichlorophenol2-methylphenol

2,000µg/mL each in CH2Cl

2, 1mL/ampul

Each 5-pk. 10-pk.31008 31008-510

w/data pack 31008-500 31008-520 31108

SV Calibration Mix #3bis(2-chloroethoxy)methane 4-chlorophenyl phenyl etherbis(2-chloroethyl)ether dimethyl phthalatebis(2-chloroisopropyl)ether di-n-butyl phthalatebis(2-ethylhexyl)phthalate di-n-octyl phthalate4-bromophenyl phenyl ether N-nitrosodimethylaminebutyl benzyl phthalate N-nitroso-di-n-propylamine2-chloronaphthalene N-nitrosodiphenylamine

2,000µg/mL each in CH2Cl

2, 1mL/ampul

Each 5-pk. 10-pk.31009 31009-510

w/data pack 31009-500 31009-520 31109

SV Calibration Mix #4carbazolehexachlorocyclopentadienedibenzofuran hexachloroethanediethyl phthalate isophorone2,4-dinitrotoluene 2-methylnaphthalene2,6-dinitrotoluene nitrobenzenehexachlorobenzene 1,2,4-trichlorobenzenehexachlorobutadiene

2,000µg/mL each in CH2Cl

2, 1mL/ampul

Each 5-pk. 10-pk.31010 31010-510

w/data pack 31010-500 31010-520 31110

EPA CLP—Semivolatiles Calibration Mixtures and Kits

3/90 and 4/89 SOW

SV Calibration Mix #5acenaphthene chryseneacenaphthylene dibenzo(a,h)anthraceneanthracene fluoranthenebenzo(a)anthracene fluorenebenzo(a)pyrene indeno(1,2,3-cd)pyrenebenzo(b)fluoranthene naphthalenebenzo(k)fluoranthene phenanthrenebenzo(ghi)perylene pyrene

2,000µg/mL each in CH2Cl

2, 1mL/ampul

Each 5-pk. 10-pk.31011 31011-510

w/data pack 31011-500 31011-520 31111

SV Calibration Mix #6aldrin endosulfan Iα-BHC endosulfan IIβ-BHC endosulfan sulfateδ-BHC endrinγ-BHC (lindane) endrin aldehyde4,4'-DDD endrin ketone4,4'-DDE heptachlor4,4'-DDT heptachlor epoxide (B)dieldrin methoxychlor

2,000µg/mL each in toluene/hexane (1:1), 1mL/ampul

Each 5-pk. 10-pk.31012 31012-510

w/data pack 31012-500 31012-520 31112

SV Calibration Mix #71,2-dichlorobenzene1,3-dichlorobenzene1,4-dichlorobenzene

2,000µg/mL each in CH2Cl

2, 1mL/ampul

Each 5-pk. 10-pk.31013 31013-510

w/data pack 31013-500 31013-520 31113

3,3'-Dichlorobenzidine2,000µg/mL each in methanol, 1mL/ampul

Each 5-pk. 10-pk.31026 31026-510

w/data pack 31026-500 31026-520 31126

Page 28: Restek Column

PATENTS & TRADEMARKSRestek patents and trademarksare the property of RestekCorporation. Other trademarksappearing in Restek literatureor on its website are the prop-erty of their respective owners.

Restek U.S. • 110 Benner Circle • Bellefonte, PA 16823 • 814-353-1300 • 800-356-1688 • fax: 814-353-1309 • www.restek.comRestek France • phone: +33 (0)1 60 78 32 10 • fax: +33 (0)1 60 78 70 90 • e-mail: [email protected] GmbH • phone: +49 (0)6172 2797 0 • fax: +49 (0)6172 2797 77 • e-mail: [email protected] Ireland • phone: +44 (0)2890 814576 • fax: +44 (0)2890 814576 • e-mail: [email protected] Japan • phone: +81 (3)6459 0025 • fax: +81 (3)6459 0025 • e-mail: [email protected] Restek U.K. LTD • phone: +44 (0)1494 563377 • fax: +44 (0)1494 564990 • e-mail: [email protected]

Lit. Cat.# 59411A© 202 Restek Corporation.